CN109415281A - Chloroform Light chlorimation is carbon tetrachloride - Google Patents
Chloroform Light chlorimation is carbon tetrachloride Download PDFInfo
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- CN109415281A CN109415281A CN201780042012.2A CN201780042012A CN109415281A CN 109415281 A CN109415281 A CN 109415281A CN 201780042012 A CN201780042012 A CN 201780042012A CN 109415281 A CN109415281 A CN 109415281A
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- Prior art keywords
- chloroform
- chlorine
- carbon tetrachloride
- reactor
- reaction
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Links
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 title claims abstract description 378
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 title claims abstract description 326
- 239000000460 chlorine Substances 0.000 claims abstract description 135
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 128
- 239000011541 reaction mixture Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 57
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 26
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 5
- 238000005911 haloform reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 87
- 239000000047 product Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 38
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000000994 depressogenic effect Effects 0.000 claims description 5
- 230000006872 improvement Effects 0.000 claims description 3
- 238000013139 quantization Methods 0.000 claims description 2
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims 1
- 239000004615 ingredient Substances 0.000 description 29
- 238000005660 chlorination reaction Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000005388 borosilicate glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006284 Kharasch reaction Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- -1 yield 100%.Therefore Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
- C07C19/03—Chloromethanes
- C07C19/041—Carbon tetrachloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of for producing carbon tetrachloride, described method includes following steps: making chlorine and haloform reaction in the reaction mixture comprising chlorine, chloroform and carbon tetrachloride in the presence of electromagnetic radiation, wherein, weight relative to reaction mixture, the concentration of chloroform is less than 5000ppm (by weight), the reaction mixture includes at least the chlorine of the stoichiometric levels relative to chloroform, which generates chloro, and reaction mixture is sufficiently mixed.
Description
This application claims the benefit of priority for the U.S. Provisional Application Serial No. 62/358,340 that on July 5th, 2016 submits,
It is totally incorporated herein by reference.
Invention field
Embodiments of the present invention are related to including the chlorination by chloroform Light chlorimation for carbon tetrachloride.
Background technique
Carbon tetrachloride is the valuable raw material for synthesizing many important commercial chemicals.In particular, carbon tetrachloride is through common
The base stock of production chloropropane is acted on, chloropropane is for producing HF hydrocarbon (hydrofluoroolefin, HFO).
Although initially reacting to form carbon tetrachloride with chlorine by chloroform, most of business methods are by carrying out chlorine to methane
Change to synthesize carbon tetrachloride.It also proposed and be by methane (such as monochloro methane, methylene chloride and chloroform) chlorination of partial oxidation
The commercial run of carbon tetrachloride.For example, U.S. Patent No. 9,169,177 disclose for the methane production four by partial oxidation
The method of chlorination carbon.In order to obtain the higher reaction selectivity to carbon tetrachloride, patent proposition, which is held conversion in, to be lower than
90%, this generates the product streams comprising chloroform and carbon tetrachloride, and the generation of monochloro methane or methylene chloride is considerably less.?
These not complete completely halogenated chloromethanes (for example, chloroform) are circulated back in reactor for further chlorination in product stream.
In view of the increase in demand to carbon tetrachloride, need to be effectively synthesized the commercial run of carbon tetrachloride.
Summary of the invention
One or more embodiments of the invention provide a kind of method for producing carbon tetrachloride, the method packet
It includes following steps: making chlorine and chloroform in the reaction mixture comprising chlorine, chloroform and carbon tetrachloride in the presence of electromagnetic radiation
Reaction, wherein relative to the weight of reaction mixture, the concentration of chloroform is less than 5000ppm (by weight), the reaction mixture
Including at least the chlorine of the stoichiometric levels relative to chloroform, which generates chloro, and wherein reaction mixture fills
Divide mixing.
Other embodiments of the present invention provide a kind of method for producing carbon tetrachloride, and the method includes walking as follows
Rapid: (i) provides reaction mixture in reactor, wherein the reaction mixture includes carbon tetrachloride, chlorine and chloroform；(ii) make
It obtains reaction mixture and is subjected to electromagnetic energy, thus convert carbon tetrachloride at least part chloroform；(iii) it is removed from reactor
Product stream, wherein the product stream includes carbon tetrachloride；It, will at least and after (iv) is the removal product stream the step of
A part of product stream returns in reactor.
Other embodiments of the present invention are related in the type for converting chloroform to by optical chlorinating reaction in carbon tetrachloride
Improvement in method makes chlorine be subjected to ultraviolet light in the presence of chloroform in the optical chlorinating reaction, and the improvement is included in sufficiently
In mixed reactor, in the carbon tetrachloride medium comprising the chlorine less than 5000ppm chloroform and at least stoichiometric levels into
Row optical chlorinating reaction, the reactor include the reaction zone for being subjected to the electromagnetic radiation that wavelength is about 200 to about 500nm.
Detailed description of the invention
Fig. 1 is the flow chart of the method for one or more embodiments according to the present invention.
Fig. 2 is the flow chart of the method for one or more embodiments according to the present invention.
Fig. 3 is the schematic diagram for carrying out the system of the method for embodiment according to the present invention.
The detailed description of illustrative embodiments
Embodiments of the present invention are at least partially based on the discovery that the method for carbon tetrachloride is produced by the Light chlorimation of chloroform.
Embodiment according to the present invention, reaction occur in carbon tetrachloride medium, and the carbon tetrachloride medium includes relative high levels
The chloroform of chlorine and low relative levels.By practicing method of the invention, it was unexpectedly found that can be to be shown to carbon tetrachloride
It writes selectivity and obtains the available level of conversion of industry.Advantageously, it has been found possible to maintain the formation of carbon trichloride low
In commercially acceptable level, the carbon trichloride is generated by two trichloromethyl group dimerization.Therefore, real according to the present invention
Applying carbon tetrachloride product caused by mode can be used as crude product stream in subsequent synthetic processes [for example, Wladyslaw Karas reacts
(Kharasch reaction)] in directly use, it is organic to remove undesirable severe chlorination without expensive purifying
Object.
Method is summarized
The general introduction of one or more embodiment of the invention can be described with reference to Fig. 1, and Fig. 1 shows chlorination
11.Carbon tetrachloride feeding flow 12 ' and chlorine feed stream 14 ' provide carbon tetrachloride 12 and chlorine 14 to introduce step 13, wherein
Carbon tetrachloride 12 and chlorine 14 merge so that the mixture of carbon tetrachloride 12 and chlorine 14 is consequently formed, and are referred to as initially mixed
Close object 15.The original mixture 15 of carbon tetrachloride and chlorine is then subjected to from electromagnetic radiation source in free radical forming step 17
18 electromagnetic radiation 18 '.Free radical forming step 17 forms the mixture 19 of chlorine, carbon tetrachloride and chlorine radical,
It is properly termed as free based mixtures 19.
Chloroform 20 is introduced free based mixtures 19 by chloroform feeding flow 20 ', to form reaction mixture 22, and is occurred anti-
Step 21 is answered, product carbon tetrachloride required for converting chloroform 20 to, and generate byproduct of reaction hydrochloric acid 24.Tetrachloro
Change carbon, chlorine and hydrochloric acid to be included in product mixtures 28, is considered the intermediate product stream from reaction step 21
28' or crude product stream 28'.Then, crude product stream 28' can be subjected to one or more extra process steps 25, for example, desorption step
Suddenly (stripping step) 25 (it may include such as air lift), by via air-flow 24 ' remove at least part chlorine and
Hydrochloric acid 24 is concentrated carbon tetrachloride 26 by the stream 26' of purifying.
In one or more embodiments, the carbon tetrachloride 26 of at least part purifying can be followed by recycle stream 29 '
It is looped back to reaction step 21.The carbon tetrachloride 26 of at least part purifying can be by the product stream 30 ' of purifying in other ways
Recycling is used as product 30.As described above, the stream 26 ' of purifying advantageously can be directly used as reaction stream in subsequent chemistry synthesis
Without distillation process, the distillation process may be needed for removing organic substance originally, for example, severe chloridized organic closes
Object is often the by-product in chlorinated organics manufacture.Nevertheless, but there is still a need for flow into product for special-purpose
Row is further purified.Therefore, certain embodiments of the invention may include that distillation process is further pure with convection current 26' progress
Change.
One alternative method scheme may refer to Fig. 2 and be described, and Fig. 2 shows chlorination 31.From into
The carbon tetrachloride 12 of stream 12 ' is combined with the electromagnetic radiation 18 ' from radiation source 18, to provide via radiation in being introduced into step 33
Medium 32.Chloroform 20 from feeding flow 20 ' merges with the chlorine 14 from feeding flow 14 ', to be formed in merging step 35
Reaction-ure mixture 34.In this step, carbon tetrachloride can optionally merge with chloroform 20 and chlorine 14.
Medium 32 (it is continuously subjected to electromagnetic radiation) via radiation and reaction-ure mixture 34 are introduced in step 37 with shape
At reaction mixture 22, reaction step 21 is generated, carbon tetrachloride (that is, chloroform is chlorinated) is converted by chloroform 20 and generates
Hydrochloric acid as byproduct of reaction.Carbon tetrachloride and hydrochloric acid are included in product mixtures 28, are considered and
The intermediate product stream 28' or crude product stream 28' of autoreaction step 21.Then, crude product stream 28' can be subjected to one or more volumes
Outer procedure of processing 25, for example, desorption procedure 25 (it may include such as air lift), by via the removal of air-flow 24 ' at least one
Part chlorine and hydrochloric acid 24 are concentrated carbon tetrachloride 26 by the stream 26' of purifying.
In one or more embodiments, at least part carbon tetrachloride 26 can be circulated back to by recycle stream 29 '
Initial step 33 and/or step 35.The carbon tetrachloride 26 of at least part purifying can be by the product stream 30 ' of purifying with other
Mode is recycled as product 30.As above refering to what is shown in Fig. 1, can be to avoid additional purifying, such as distill.And in certain implementations
In mode, it may be necessary in addition purify, including distillation.
System for carrying out chloroform chlorination
System for carrying out the method for the present invention can be described with reference to Fig. 3, and Fig. 3 is shown for carrying out chlorination
System 51.System 51 includes reaction vessel 53, and the reaction vessel 53 includes entrance 57, outlet 61, lamp 63, agitating element
65 and product exit 67.
It, will be by the chloroform 54 of chloroform feeding flow 54 ' and for example, by the four of recycle stream 75 ' according to illustrative embodiments
Chlorination carbon merges, to form reactant pre-composition.Then merged with reactant pre-composition by the chlorine 52 of feeding flow 52 ' (for example,
Pass through online sprayer), to form reaction-ure mixture in stream 77 ', the reactant pre-composition includes chloroform and four chlorinations
Carbon.It, can the mixing or in other ways in mixing arrangement (for example, online mixer 55) as shown in figure 3, before introducing chlorine
Stir chloroform and carbon tetrachloride.In not shown other embodiment, it is contained in stream 77 ' and contains chlorine, chloroform and tetrachloro
The mixture for changing carbon can be similarly stirred before being introduced into reactor 53.
Then, feeding flow 77 ' is introduced into reactor 53 by entrance 57.As described above, the electromagnetic radiation from lamp 63 is led
Chlorination reaction is caused, chloroform is converted into carbon tetrachloride as a result,.Carbon tetrachloride product obtained is as product stream 66 ' from reactor
53 are removed by outlet 67, and product stream 66' is also referred to as crude product stream 66'.Product stream 66 ' can also include chloroform, chlorine and chlorine
Change one of hydrogen or a variety of and low relative levels other by-products.Gaseous by-product (such as hydrogen chloride and chlorine) can lead to
It crosses outlet 61 to remove from reactor 53, to form stream 79'.The stream can be neutralized, for disposing or further separating,
To separate chlorine and hydrochloric acid, other synthesis chemical processes then can be used for.
Crude product stream 66 ' can reach tank 69 by path, and tank 69 may include degassing tank, and wherein crude product stream 66' can be with
By being concentrated via air-flow 69' removal light component (such as chlorine and hydrogen chloride), air-flow 69 ' can merge with stream 79'.Example
Such as, by pump 71, the crude product stream 66 ' of the carbon tetrachloride containing concentration can be by path by recirculation circuit 71 ' via four
Chlorination carbon feeding flow 75 ' returns to reactor 53.Alternatively, the crude product stream of concentration can pass through carbon tetrachloride product stream by path
73 ' leave system for storing and further using.In one or more embodiments, carbon tetrachloride product stream 73 ' can
To be subjected to the other electromagnetic radiation by for example refining the offers such as UV reactor (polishing UV reactor) (as related to herein
And described in lamp 63), to carry out Light chlorimation to any remaining chloroform in product stream.In one or more embodiments
In, other chlorine can be added into the product stream handled in the downstream finishing reactor.
It should be appreciated that according to some embodiments of the present invention, recirculation circuit 71' be it is optional, because of crude product stream
66' can directly reach other techniques (that is, stream 66' can directly reach 73' by path) by path.However, in these implementations
In mode, it is necessary to use carbon tetrachloride alternate source as reaction medium.
Therefore it should be understood that method (and system) of the invention can be used as continuation method and be operated, wherein will react
Object continuous feed continuously removes product into reactor and from reactor.In addition, require can be by for the technique of carbon tetrachloride
Product stream from system meets (for example, carbon tetrachloride product stream 66' can be circulated back to reactor by inlet flow 75'
53).In one or more embodiments, in the system initial start for needing carbon tetrachloride external source (such as carbon tetrachloride 12)
Later, method of the invention can meet from the carbon tetrachloride of system (such as being recycled by circuit 71') from circulation and be greater than 90%
The carbon tetrachloride demand for system operatio, in other embodiments, meet be greater than 95% four for system operatio
Chlorination carbon demand meets the carbon tetrachloride demand for system operatio greater than 99% in other embodiments.
It should also be understood that in the case of without departing from the present invention, can be carry out various modifications to system 51.For example, chlorine 52
Reactor 53 can be directly injected by respective feeding flow with chloroform 54, without before introducing reaction vessel 53 to chlorine
52 and chloroform 54 be pre-mixed.In a specific embodiment, chloroform feeding flow 54' can be introduced under the liquid level in reactor
Side (for example, passing through dip-tube).In these or other embodiment, equally chlorine feeding flow 52' can be introduced below liquid level,
For example, being introduced by sprayer.It, can be first by separated and different feeding flow and tetrachloro in one or more embodiments
Change carbon to merge, then be introduced directly into reactor 53.Moreover, reactor 53 can be configured to provide from reactor bottom to top
Material flowing, as shown generally in Figure 3 or material flowing can in turn with the top of reactor receive input and
Product is taken out from reactor bottom.
In one or more embodiments, entrance 57 may include dispersal device (for example, sprayer or dip-tube), and
And container 53 may include multiple entrance (not shown)s.
In one or more embodiments, container 53 may include single lamp, as shown in figure 3, its may include
Multiple lamps.In one or more embodiments, lamp 63 may include ultraviolet radiator, laser and light emitting diode.Specific real
It applies in mode, the lamp includes mercury vapour arc lamp, such as Hanovia lamp (Hanovia lamp).In one or more embodiments
In, one or more lamps (for example, lamp 63) can be partially immersed in the reaction medium accommodated in container 53 or they can
To be completely submerged in reaction medium.In not shown other embodiment, lamp can except inside reactor, but still
Positioned at making place of the required electromagnetic radiation into reactor media.
Moreover, reaction vessel 53 can be equipped with humidity control system, for example, heating/cooling jacket.In one or more
In embodiment, agitating element 65 may include single mechanical agitator, as shown in figure 3, multiple stirrings can use
Device.As known in the art, various combination constructions can be used, the mixer including being installed on top and bottom.
In one or more embodiments, reactor 58 is configured to include dark space, the dark space be in reactor without
By can perception level electromagnetic radiation region, the electromagnetic radiation cause it is as described herein needed for optical chlorinating reaction.Dark space has
Time and space are provided for inlet flow 77' sharply so that its elder generation is in the higher volume of carbon tetrachloride being contained in reactor 53
In it is thinning and be sufficiently mixed, then in the presence of suitable electromagnetic radiation, make chlorine become free radical and/or make chloro/chlorine from
It is reacted by base with chloroform.It will be understood by those skilled in the art that dark space can be created by using number of mechanisms.For example, can
To place physical obstacle in the reactor, thus the electromagnetic radiation that protection zone is issued from lamp 63.Alternatively, or and object
Obstacle combination is managed, dark space can be formed by providing enough distances between lamp 63 and the required position of dark space.This field
It should be understood to the one skilled in the art that entrance 57 be preferably located on it is in dark space or adjacent with dark space.
It should be appreciated that on startup, carbon tetrachloride is initially added into reactor 53 and is reacted with formed therein
Initial medium.In one or more embodiments, react start when reactor free or substantially free of chloroform, to avoid
There is excessive chloroform relative to chlorine at any one moment of reaction.Once reaction carries out, the chlorine and chloroform in reactor 53
And therefore the appropriate balance of carbon tetrachloride can be inputted by adjusting the chlorine for entering reactor 53, chloroform and optional carbon tetrachloride
It maintains, the balance will hereinafter be described.
Although describing the system with reference to a specific embodiment of the invention, those skilled in the art can modify this
System is to adapt to other techniques as described herein without excessively calculating or testing.
The characteristic of carbon tetrachloride feeding flow
In one or more embodiments, carbon tetrachloride feeding flow (for example, 12', 75') is substantially carbon tetrachloride,
Refer to the feeding flow of the ingredient in addition to carbon tetrachloride not comprising significant quantity.In one or more embodiments, four chlorinations
Carbon feeding flow (for example, 12', 75') is made of carbon tetrachloride substantially, is referred to and is free of other materially affect embodiment party of the present invention
The composition of other ingredients of the fundamental characteristics and novel characteristics of formula.In one or more embodiments, carbon tetrachloride charging
Stream (for example, 12', 75') is made of carbon tetrachloride.In one or more embodiments, carbon tetrachloride is four chlorination of technical grade
Carbon.In one or more embodiments, carbon tetrachloride feeding flow 12', 75' includes about 99.9 weight % to about 100 weight %
Carbon tetrachloride.In one or more embodiments, carbon tetrachloride feeding flow (for example, 12', 75') includes to be lower than 7000ppm
Chlorinated organics ingredient other than carbon tetrachloride, in other embodiments comprising lower than 6000ppm in addition to tetrachloro
Change the chlorinated organics ingredient except carbon, in other embodiments comprising lower than 5500ppm other than carbon tetrachloride
Chlorinated organics ingredient, in other embodiments comprising the chlorinated organics other than carbon tetrachloride lower than 5000ppm
Ingredient, in other embodiments comprising the chlorinated organics ingredient other than carbon tetrachloride lower than 2500ppm, other
Comprising the chlorinated organics ingredient other than carbon tetrachloride lower than 1000ppm in embodiment, in other embodiments
The chlorinated organics ingredient other than carbon tetrachloride comprising being lower than 750ppm, in other embodiments comprising being lower than
The chlorinated organics ingredient other than carbon tetrachloride of 500ppm, in other embodiments comprising lower than 100ppm in addition to
Chlorinated organics ingredient except carbon tetrachloride.
The characteristic of chlorine feeding flow
In one or more embodiments, chlorine feeding flow (for example, 14', 52') is substantially chlorine, is referred to not comprising aobvious
The feeding flow of the ingredient in addition to chlorine of work amount.In one or more embodiments, chlorine feed stream (for example, 14',
It 52') is made of substantially chlorine, refers to and be free of the fundamental characteristics and novel characteristics of other materially affect embodiment of the present invention
Other ingredients composition.In one or more embodiments, chlorine feed stream (for example, 14', 52') is made of chlorine.
In one or more embodiments, chlorine feeding flow (for example, 14', 52') includes about 99.5 volume % to about 100 volume %'s
Chlorine.In one or more embodiments, chlorine feeding flow (for example, 14', 52') include less than 5000ppm in addition to chlorine
Ingredient, in other embodiments comprising the ingredient in addition to chlorine less than 1000ppm, in other embodiments comprising small
In the ingredient in addition to chlorine of 750ppm, in other embodiments comprising the ingredient in addition to chlorine less than 500ppm.
In one or more embodiments, before introducing system, chlorine feed stream (for example, 14', 52') with nitrogen or
Other inert medias such as argon gas is purged.Therefore, in one or more embodiments, chlorine feed stream (for example, 14',
It 52') is substantially free of oxygen, refers to the feeding flow without significant quantity oxygen.In one or more embodiments, chlorine feeding flow (example
Such as, 14', 52') comprising the oxygen less than 2500ppm, in other embodiments comprising the oxygen less than 1000ppm, in other implementations
Comprising the oxygen less than 750ppm in mode, in other embodiments comprising the oxygen less than 500ppm, in other embodiments
Oxygen comprising being less than 250ppm.
The characteristic of chloroform charging
In one or more embodiments, chloroform feeding flow 20', 54' is substantially chloroform, is referred to not comprising significant quantity
The ingredient in addition to chloroform feeding flow.In one or more embodiments, chloroform feeding flow 20', 54' is substantially by chloroform
Composition refers to and is free of the group of the fundamental characteristics of other materially affect embodiment of the present invention and other ingredients of novel characteristics
Close object.In one or more embodiments, chloroform feeding flow 20', 62 are made of chloroform.In one or more embodiments
In, chloroform is technical grade chloroform.In other embodiments, using fluorine carbon grade (fluorocarbon-grade) chloroform.At it
In his embodiment, chloroform may include the charging from other synthesis technologies (e.g., chloromethanes produces).One or more real
It applies in mode, chloroform feeding flow 20', 54' includes the chloroform of about 99.8 weight % to about 100 weight %.One or more real
It applies in mode, chloroform feeding flow 20', 62 include the ingredient other than chloroform less than 5000ppm, in other embodiments
The ingredient other than chloroform comprising being less than 2500ppm includes in other embodiments less than 2000ppm in addition to chloroform
Except ingredient, in other embodiments comprising less than 1000ppm the ingredient other than chloroform, in other embodiment
In comprising the ingredient other than chloroform less than 750ppm, in other embodiments comprising less than 500ppm in addition to chloroform
Except ingredient.
The characteristic of reaction mixture
In one or more embodiments, carbon tetrachloride, chlorine, hydrogen chloride and chloroform and remaining by-product will be contained
The reaction mixture (for example, content of reaction mixture 22 or reactor 53) of (such as severe chlorinated organics) be maintained at so that
Carbon tetrachloride is kept under the temperature and pressure of liquid.It will be understood by those skilled in the art that higher operating pressure is higher by permission
Operation temperature because method of the invention preferably carries out in the liquid phase.
In one or more embodiments, during reaction or chlorinating step (such as reaction step 21) or optionally exist
Before this, reaction mixture (for example, content of reaction mixture 22 or reactor 53) is maintained at the temperature greater than 10 DEG C
Under, at a temperature of being maintained in other embodiments greater than 15 DEG C, and it is maintained in other embodiments greater than 20 DEG C
At a temperature of.In these or other embodiment, before or during reaction step, all reaction mixture is maintained at and is less than
At a temperature of 70 DEG C, at a temperature of being maintained in other embodiments less than 60 DEG C, and keep in other embodiments
Less than 50 DEG C at a temperature of.In one or more embodiments, before or during reaction step, all by reaction mixture
It is maintained at a temperature of about 10 DEG C to about 70 DEG C, is maintained at a temperature of about 15 DEG C to about 60 DEG C in other embodiments, or
It is maintained at a temperature of about 20 DEG C to about 50 DEG C in other embodiments.It is in one or more embodiments, reaction is mixed
It closes object (for example, content of reaction mixture 22 or reactor 53) to be maintained under certain temperature and pressure, the temperature and pressure
Power is enough to keep the chlorine and chloroform of relative high levels in carbon tetrachloride medium.
In one or more embodiments, (for example, before or during step 21), it will be reacted in reaction or chlorinating step
Mixture (for example, content of reaction mixture 22 or reactor 53) is maintained under the pressure greater than 0.8 atmospheric pressure, at it
It is maintained under the pressure greater than 0.9 atmospheric pressure, and is maintained in other embodiments greater than 0.95 in its embodiment
Under the pressure of a atmospheric pressure.In these or other embodiment, before or during reaction step, all reaction mixture is protected
It holds under the pressure less than 15 atmospheric pressure, is maintained under the pressure less than 10 atmospheric pressure in other embodiments, and
It is maintained under the pressure less than 5 atmospheric pressure in other embodiments.In one or more embodiments, in reaction step
Before or during, reaction mixture is all maintained at about 0.8 atmosphere and is depressed under the pressure of about 15 atmospheric pressure, in other implementations
It is maintained at about 0.9 atmosphere in mode to be depressed under the pressure of about 10 atmospheric pressure, or is maintained in other embodiments about
0.95 atmosphere is depressed under the pressure of about 5 atmospheric pressure.
In one or more embodiments, reaction or chlorinating step (for example, before or during step 21), all will be anti-
Mixture (for example, content of reaction mixture 22 or reactor 53) is answered to be maintained at stirring.Implement in one or more
In mode, stirring is enough to obtain (such as reactor 53) turbulent flow of the reactor by reacting.Implement in one or more
In mode, stirring is enough to obtain turbulent flow, and the turbulent flow can quantify with the Reynolds number greater than 4000, in other embodiments
Quantify the Reynolds number for having greater than 10000, and quantization has the Reynolds number greater than 20000 in other embodiments.At this
In a little or other embodiment, in reaction step, (such as before or during step 21), reaction mixture is all kept stirring to mention
For turbulent flow, the turbulent flow can quantify the Reynolds number with about 4000 to about 30000, can quantify to have in other embodiments
There is the Reynolds number of about 8000 to about 28000, or the thunder with about 10000 to about 26000 can be quantified in other embodiments
Promise number.In one or more embodiments, Light chlorimation process of the invention carries out in reactor (such as reactor 53), institute
Stating reactor is sufficiently stirred to approach the well-mixed reactor of ideal continuous stirred tank reactor (CSTR).
As described above, by make in the presence of ultraviolet light the basic transient response of chloroform at the amount of carbon tetrachloride and in a manner of by chloroform
Being introduced into reaction mixture, (for example, the content of mixture 22 or reactor 53, therefore feed rate is adjusted in reactor
Chloroform concentration.It was unexpectedly found that reaction step (such as step 21) during and before at once dilution and dispersion can be with four
The miscible chloroform of chlorination carbon is the key parameter for obtaining favourable outcome of the present invention.
In one or more embodiments, the feed rate of chloroform to reactor (for example, reactor 53) can be opposite
Carbon tetrachloride in reactor is quantified.In one or more embodiments, the feed rate of chloroform is greater than 10 pounds
Carbon tetrachloride in every 1000 pounds of reactors per hour is in other embodiments every 1000 pounds of reactions per hour greater than 15 pounds
Carbon tetrachloride in device is in other embodiments the carbon tetrachloride in every 1000 pounds of reactors per hour greater than 25 pounds,
It is the carbon tetrachloride in every 1000 pounds of reactors per hour greater than 35 pounds in other embodiment, is in other embodiments big
Carbon tetrachloride in 45 pounds per hour every 1000 pounds of reactors is in other embodiments greater than 55 pounds per hour every 1000
Carbon tetrachloride in pound reactor is in other embodiments four chlorinations in every 1000 pounds of reactors per hour greater than 65 pounds
Carbon is in other embodiments the carbon tetrachloride in every 1000 pounds of reactors per hour greater than 75 pounds, in other embodiment
In for the carbon tetrachloride in every 1000 pounds of reactors per hour greater than 85 pounds, in other embodiments for per hour greater than 95 pounds
Carbon tetrachloride in every 1000 pounds of reactors, in other embodiments for greater than 110 pounds per hour in every 1000 pounds of reactors
Carbon tetrachloride, be in other embodiments the carbon tetrachloride in every 1000 pounds of reactors per hour greater than 120 pounds.At these
Or in other embodiment, the feed rate of chloroform is the carbon tetrachloride in every 1000 pounds of reactors per hour less than 1000 pounds,
It is in other embodiments the carbon tetrachloride in every 1000 pounds of reactors per hour less than 800 pounds, in other embodiments
For the carbon tetrachloride in every 1000 pounds of reactors per hour less than 650 pounds, in other embodiments for per hour less than 500 pounds
Carbon tetrachloride in every 1000 pounds of reactors, in other embodiments for less than 250 pounds per hour in every 1000 pounds of reactors
Carbon tetrachloride, be in other embodiments the carbon tetrachloride in every 1000 pounds of reactors per hour less than 200 pounds, other
Be the carbon tetrachloride in every 1000 pounds of reactors per hour less than 150 pounds in embodiment, in other embodiments for less than
125 pounds of carbon tetrachloride in every 1000 pounds of reactors per hour are in other embodiments less than 100 pounds per hour every 1000
Carbon tetrachloride in pound reactor is in other embodiments four chlorinations in every 1000 pounds of reactors per hour less than 80 pounds
Carbon is in other embodiments the carbon tetrachloride in every 1000 pounds of reactors per hour less than 60 pounds, in other embodiment
In for the carbon tetrachloride in every 1000 pounds of reactors per hour less than 40 pounds, in other embodiments for per hour less than 30 pounds
Carbon tetrachloride in every 1000 pounds of reactors, in other embodiments for less than 25 pounds per hour in every 1000 pounds of reactors
Carbon tetrachloride.In one or more embodiments, the feed rate of chloroform is about 10 to about 1000 pounds every per hour 1000 pounds
Carbon tetrachloride in reactor is four in about 25 to about 650 pounds of 1000 pounds of reactors every per hour in other embodiments
Chlorination carbon is the carbon tetrachloride in about 55 to about 200 pounds of 1000 pounds of reactors every per hour in other embodiments.
In one or more embodiments, the dilution of chloroform can also based on reaction mixture (for example, mixture 22 or
The content of reactor 53) in the amount of chloroform quantified.For example, the concentration of chloroform can be based on opposite in reaction mixture
Quantify in the chloroform weight of reaction mixture weight, reaction mixture includes carbon tetrachloride, chlorine, chlorination in reaction mixture
Hydrogen and chloroform.It should be understood to the one skilled in the art that this tittle (that is, chloroform in reaction mixture) can be by reactor effluent
Chloroform amount in (that is, exporting) is measured the chloroform in the reactor effluent in the reactor being sufficiently stirred to determine
Amount is equal to chloroform amount in the reaction region, and wherein reaction zone refers to that in reaction medium, (that is, in reactor) chloroform occurs
The position of chlorination (that is, electromagnetic radiation that reaction mixture is subjected to appropriate wavelength).In one or more embodiments, based on anti-
The total weight of mixture is answered, the concentration of chloroform is the chloroform less than 5000ppm (by weight) in reaction mixture, in other realities
It applies for the chloroform less than 4000ppm in mode, is in other embodiments the chloroform less than 3000ppm, and in other realities
It applies in mode as the chloroform less than 2000ppm.In one or more embodiments, the overall weight based on reaction mixture,
The chloroform that the concentration of chloroform is about 1 to about 5000ppm in reaction mixture is about 50 in other embodiments to about
The chloroform of 3000ppm, and be in other embodiments about 100 to about 2000ppm chloroform.
It is as suggested above, during reaction step (for example, reaction step 21) existing for chlorine amount or in other words anti-
The amount for answering chlorine present in mixture is considered as practicing important parameter of the invention.In one or more embodiments, with
Chlorine is introduced reaction mixture (for example, container 53) by a certain amount of and mode, and described a certain amount of and mode provides relatively to reaction
It is at least the chlorine of stoichiometry or the amount more than stoichiometry in chloroform.In one or more embodiments, reacted
Temperature and pressure under, the cl concn in reaction medium (that is, carbon tetrachloride) is in saturated level of the chlorine in carbon tetrachloride.?
In one or more embodiments, the amount of chlorine is enough to keep considerable in the head space of reactor in reactor (such as reactor 53)
Level of chlorine.For it will be fed to reactor relative to the excessive chlorine of chloroform, the cl concn in reactor can be with the time
Passage continue to increase, until reaching saturated level relative to the temperature and pressure in reactor, although passing through recirculation circuit
Carrying out recycling to carbon tetrachloride can be used for adjusting the amount of chlorine in reactor.
In one or more embodiments, the amount for introducing the chlorine of reaction mixture can be based on the chlorine for being fed into reactor
Quantified with the molar ratio of chloroform.In one or more embodiments, it is fed into such as chlorine of reactor 53 and chloroform
Molar ratio be greater than 1.00:1.00, in other embodiments for greater than 1.02:1.00, in other embodiments for greater than
1.04:1.00.In one or more embodiments, the molar ratio of chlorine and chloroform is about 1.00:1.00 to about 1.10:1.00,
In other embodiments it is about 1.01:1.00 to about 1.08:1.00, is in other embodiments about 1.02:1.00 to about
1.06:1.00.
In these or other embodiment, the amount of the chlorine used in the methods of the invention can be based in reaction mixture
The concentration of chlorine quantifies.It should be understood to the one skilled in the art that this tittle (that is, chlorine in reaction mixture) can be by flowing out reactor
The amount of chlorine in object (that is, exporting) is measured the chlorine in the reactor effluent in the reactor being sufficiently stirred to determine
Amount be equal to the amount of chlorine in the reaction region, wherein reaction zone refers to that in reaction medium, (that is, in reactor) chloroform is sent out
The position of raw chlorination.In one or more embodiments, the total weight based on reaction mixture, the concentration of chlorine is in effluent
Greater than 0.01 weight %, in other embodiments for greater than 0.1 weight %, in other embodiments for greater than 0.3 weight
% is measured, in other embodiments for greater than 0.6 weight %, in other embodiments for greater than 1.2 weight %, in other realities
It applies in mode as greater than 1.5 weight %, in other embodiments greater than 1.8 weight %, to be in other embodiments big
In 2.0 weight %. in these or other embodiment, the concentration of chlorine is under given temperature and pressure in reactor effluent
Saturated level, in other embodiments, the total weight based on reaction mixture, for less than 5 weight %, in other embodiment party
For less than 4.6 weight % in formula, and in other embodiments for less than 4.2 weight %.In one or more embodiments
In, the total weight based on reaction mixture, the concentration of chlorine is about 0.01 weight % to being saturated in reaction mixture, in other implementations
It is about 0.1 weight % to about 5 weight % in mode, is in other embodiments about 0.3 weight % to about 5 weight %, at it
It is about 1.8 weight % to about 4.6 weight % in its embodiment, and is in other embodiments about 2.0 weight % to about
4.2 weight %.
The characteristic of electromagnetic radiation
In one or more embodiments, used electromagnetic radiation by lamp 63 (for example, produced when practicing the present invention
It is raw) characteristic include about 200 to about 500nm wavelength, be in other embodiments about 200 to about 400nm wavelength,
It is about 280 to about 380nm wavelength in other embodiment, is in other embodiments about 300 to about 350nm wavelength.
In these or other embodiment, the characteristic of electromagnetic radiation is the Wavelength distribution based on relative intensity, wherein about 50% to about
60% intensity have about 280nm to about 435nm wavelength, in these or other embodiment about 40% to about 50% it is strong
The wavelength with about 300nm to about 380nm is spent, the intensity of about 20% to about 30% has about in these or other embodiment
The wavelength of 330nm to about 370nm.In one or more embodiments, electromagnetic radiation includes ultraviolet light.
In one or more embodiments, electromagnetic radiation is provided by one or more electroluminescent lamps, and the electroluminescent lamp is in 40W
It works under to about 20,000W, works at about 75W to about 18,000W, exist in other embodiments in other embodiments
It works under about 100W to about 10000W.In one or more embodiments, electromagnetic radiation is provided by one or more mercury lamps.?
In specific embodiment, electromagnetic radiation is provided by Hanovia mercury vapour arc lamp.
The characteristic of product stream
As described above, carbon tetrachloride crude product stream (for example, stream 28' and 66') include required carbon tetrachloride product, chlorine and
Hydrogen chloride and remaining by-product (such as severe chlorinated organics).In one or more embodiments, these product stream (examples
Such as, 28', 66') it is substantially carbon tetrachloride, chloroform, hydrogen chloride and optional chlorine, refer to and removes four chlorinations not comprising significant quantity
The product stream of ingredient except carbon, chloroform, hydrogen chloride and optional chlorine.In one or more embodiments, product stream (example
Such as, 28', 66') it is made of substantially carbon tetrachloride, optional chloroform, optional hydrogen chloride and optional chlorine, refer to be free of and incite somebody to action
In addition the composition of the fundamental characteristics of materially affect embodiment of the present invention and other ingredients of novel characteristics.In one or more
In embodiment, product stream (for example, 28', 66') is by carbon tetrachloride, optional chloroform, optional hydrogen chloride and optional chlorine group
At.
In one or more embodiments, product stream (for example, 28', 66') includes to remove four chlorinations less than 2500ppm
Chlorinated hydrocabon (for example, carbon trichloride) except carbon, the chlorinated hydrocabon (example in addition to carbon tetrachloride for including in other embodiments
Such as, carbon trichloride) it is less than 1000ppm, it is less than 500ppm in other embodiments, is less than in other embodiments
250ppm is less than 100ppm (hundred a ten thousandth parts by weight) in other embodiments.
In one or more embodiments, product stream (for example, 28', 66') includes less than 2500ppm in addition to tetrachloro
Change the ingredient except carbon, hydrogen chloride and chlorine, include in other embodiments other than carbon tetrachloride, hydrogen chloride and chlorine
Ingredient is less than 1000ppm, is less than 750ppm in other embodiments, is less than (million points of 500ppm in other embodiments
One of parts by weight).
In one or more embodiments, product stream (for example, 28 ', 66 ') characteristic is advantageous low-level chloroform,
This is the high symbol of reaction yield.In one or more embodiments, relative to chloroform, reaction yield be greater than 90.00%,
In other embodiments for greater than 92.00%, in other embodiments for greater than 95.00%, in other embodiments
For greater than 97.00%, in other embodiments for greater than 98.00%, in other embodiments for greater than 99.00%,
For greater than 99.50% in other embodiment, in other embodiments in a specific embodiment greater than 99.99%., phase
For chloroform, yield 100%.Therefore, product stream 28 ', 66 ' includes the chloroform less than 6000ppm, in other embodiments
Chloroform comprising being lower than 5500ppm, in other embodiments comprising the chloroform lower than 5000ppm, in other embodiments
Chloroform comprising being lower than 4500ppm, in other embodiments comprising the chloroform lower than 4000ppm, in other embodiments
Chloroform comprising being lower than 3000ppm, in other embodiments comprising the chloroform lower than 2000ppm, in other embodiments
Chloroform comprising being lower than 1000ppm wraps in other embodiments in other embodiments comprising the chloroform lower than 500ppm
Containing the chloroform for being lower than 250ppm, in other embodiments comprising the chloroform lower than 100ppm, include in other embodiments
Chloroform lower than 50ppm, in other embodiments comprising the chloroform lower than 10ppm (hundred a ten thousandth parts by weight).
Reaction mechanism
As the proposed, the mode of this method and sequence are considered promoting in any side reaction (such as two of chloroform
Poly- reaction) chlorine radical is formed before and makes these free radicals and haloform reaction, to improve the selectivity of reaction.It is not intended to
It is any particular theory, during reaction is considered betiding one or more steps of the invention below.
Cl2+ h ν → 2Cl* (1) causes
CHCl3+Cl*→CCl3*+HCl (2) is transmitted
CCl3*+Cl2→CCl4+ Cl* (3) transmitting
CCl3*+CCl3*→C2Cl6(4) it terminates
CCl3*+Cl*→CCl4(5) it terminates
Cl*+Cl*→Cl2(6) it terminates.
Reaction 1-3 is by chloroform and chlorine conversion be carbon tetrachloride and HCl by-product desirable route.Reaction 5 generates institute
Product is needed, but cost is to make radical reaction chain termination.Reaction 4 terminates the chain, and including passing through two trichloromethyl groups
Dimerization forms carbon trichloride；The present invention substantially avoids the reaction.Reaction 6 makes to react chain termination, but there is provided chlorine, described
Chlorine can generate free radicals again in the presence of initiator (such as UV light).
Industrial feasibility
In one or more embodiments, crude product stream (for example, stream 28' or 66', 73') can be in chloridized organic
It closes and is used in the synthesis of object.As noted above, the method for the one or more embodiments of the present invention advantageously provides product
Stream, the product stream can swim in synthesis technology in these lower and directly use, without independent process (for example, distilation steps)
To remove the organic by-products (such as carbon trichloride) of more severe chlorination.
In one or more embodiments, the carbon tetrachloride of embodiment production can be used as crude product according to the present invention
Stream is directly combined with alkene (for example, ethylene or vinyl chloride), and is reacted in the presence of suitable catalyst to form chlorine third
Alkane and/or chloropropene.In this regard, U.S. Patent No. 6,187, No. 978 and U.S. Patent No. 6,313,360 and the U.S.
Disclose No. 2012/0310020, U.S. Publication the 2009/0216055th and U.S. Publication the 2004/0225166th be by drawing
Be included in herein.
In order to illustrate implementation of the invention, following embodiment has been prepared and tested.However, embodiment is not construed as pair
The limitation of the scope of the invention.Claim will be used to limit the present invention.
Embodiment
Embodiment 1-5
All reactions in embodiment 1 to 5 are in water-cooled quartz submergence lamp source (Ace#7874-38) with jacketed
It is carried out in 1 liter of Pyrex stirred reactor (Ace reactor #7864-12) of jacketed.Mercury vapour arc lamp is pressed in 450 watts
(Ace#7825-35) illumination is provided.Ensure that reactor is sufficiently carried out mixing using magnetic stir bar；It calculates: in reactor
Mixing condition by generate about 24,400 Reynolds number.Each experiment carries out in about 6 hours time intervals.Using 30m ×
0.53mm DB-624 column and thermal conductivity detector (TCD) (TCD) analyze embodiment by gas-chromatography.By to carbon trichloride
Concentration (the unique undesirable by-product detected) is measured, calculates the percentage for forming its consumed chloroform, and from
The percentage is subtracted in 100% to calculate selectivity.Related data from each embodiment is summarized in table 1 below.
Embodiment 1
1158 grams of mixtures are added into reactor, the mixture contains the chloroform and 95.6 weight % of 4.4 weight %
Carbon tetrachloride.Reaction temperature is maintained at 35 DEG C.Open UV lamp.After five minutes, 100 weights are fed with the rate of 0.29 gram/minute
The chloroform of % is measured, and the chlorine of 100 weight % is bubbled in solution with the rate of 0.18 gram/minute, lasts 6 hours.Chlorine with
70% for react required stoichiometry is fed.In 6 hours time spans, it is sampled per hour.Chlorine
The imitative selective determination to carbon tetrachloride is 65.2%, and surplus is the chloroform for generating carbon trichloride.The data collected per hour are aobvious
It shows: not changing other than normal experiment variation occurs at any time for selectivity.
Embodiment 2
The carbon tetrachloride of 1196 gram of 100 weight % is added into reactor.Reaction temperature is maintained at 35 DEG C.Open UV
Lamp.After 4 minutes, the chloroform of 100 weight % is fed with the rate of 0.30 gram/minute, and with the rate of 0.18 gram/minute by 100
The chlorine of weight % is bubbled in solution, lasts 10 minutes 6 hours.Chlorine with for react required stoichiometry carry out into
Material.It samples per hour.Chloroform is and to be converted into the chloroform of carbon trichloride close to 100% to the selective determination of carbon tetrachloride
Less than 0.003% (can not be detected at method detectable limit).The data collected per hour are shown: at any time in addition to selectivity
Occur not change except normal experiment variation.
Embodiment 3
The carbon tetrachloride of 1190 gram of 100 weight % is added into reactor.Reaction temperature is maintained at 25 DEG C.Open UV
Lamp.After 4 minutes, the chloroform of 100 weight % is fed with the rate of 0.30 gram/minute, and with the rate of 0.18 gram/minute by 100
The chlorine of weight % is bubbled in solution, lasts 5 hours.Chlorine for react required stoichiometry to be fed.Per small
When sample.Chloroform is close to 100% to the selective determination of carbon tetrachloride, and the chloroform for being converted into carbon trichloride is less than
0.003% (can not be detected at method detectable limit).The data collected per hour are shown: in addition to selectivity occurs at any time
Do not change except normal experiment variation.
Embodiment 4
The carbon tetrachloride of 1207 gram of 100 weight % is added into reactor.Reaction temperature is maintained at 35 DEG C.Chlorine is with 0.18
The rate of gram/minute is bubbled.UV lamp is opened after 30 minutes.After after five minutes, 100% chloroform is with the rate of 0.31 gram/minute
Charging.Chlorine is to be more than to be fed for react the amount of required stoichiometry.It samples per hour.Chloroform is to carbon tetrachloride
Selective determination be and to be converted into the chloroform of carbon trichloride less than 0.003% (at method detectable limit close to 100%
It can not detect).The data collected per hour are shown: not being become other than normal experiment variation occurs at any time for selectivity
Change.
Embodiment 5
1225 grams of mixtures are added into reactor, the mixture contains about 5000ppm (by weight) chloroform, and
Remaining as carbon tetrachloride.Reaction temperature is maintained at 35 DEG C.Open UV lamp.After five minutes, it is fed with the rate of 0.30 gram/minute
The chloroform of 100 weight %, and the chlorine of 100 weight % is bubbled in solution with the rate of 0.18 gram/minute, last 5 hours.
Chlorine is fed with 94% for react required stoichiometry.It samples per hour.Selectivity of the chloroform to carbon tetrachloride
It is measured as 81.4%, surplus is the chloroform for generating carbon trichloride.The data collected per hour are shown: at any time in addition to selectivity
Occur not change except normal experiment variation.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Pounds Per Hour CHCl3/1000 pounds of CCl4 | 14.97 | 15.26 | 14.87 | 15.49 | 14.67 |
| Molar ratio (Cl2:CHCl3) | 0.70 | 1.0 | 1.02 | 1.07 | 0.94 |
| Initial CHCl3 (weight %) in reactor | 4.4% | 0.0% | 0.0% | 0.0% | 0.5% |
| Temperature, DEG C | 35 | 35 | 25 | 35 | 35 |
| Borosilicate glass optical filter on lamp | It is no | It is no | It is no | It is no | It is no |
| CHCl3 conversion ratio | 88.9% | 100.0% | 99.9% | 100.0% | 93.8% |
| To the selectivity of CCl4 | 65.2% | 100.0% | 100.0% | 100.0% | 81.4% |
It is in table 1 statistics indicate that, embodiment 1 and 5 is not belonging to practical framework of the invention, because of reaction conversion ratio and to four
The selectivity of chlorination carbon is lower than acceptable level.It needs to carry out product stream by the product stream that embodiment 1 and 5 obtains further
Distillation is to remove carbon trichloride.Embodiment 2,3 and 4 provides very favorable as a result, this shows to deposit during embodiment 1 and 5
Excess chloroform negative effect is produced to reaction.
Embodiment 6-9
For embodiment 6-9, reactor used system in embodiment 1-5 is improved to provide circulation loop, so that
Chloroform can merge with the carbon tetrachloride outside reactor, then can introduce instead by the blend of chloroform, carbon tetrachloride and chlorine
It answers and chlorine is bubbled into the mixture before device.Ensure that reactor is sufficiently carried out mixing using magnetic stir bar；It calculates: anti-
Answer mixing condition in device by generate about 20,000 Reynolds number.Each experiment carries out in about 90 minutes time intervals.It will produce
Object is transferred in product receiver from reactor head extraction, with the liquid bulk kept constant in the reactor in each experiment
Product.Using 100 watts of middle pressure mercury vapor lamps (Ace#7825-30), equipped with borosilicate glass optical filter (Ace#7835 44) with
So that the attenuation of lower wavelength.Related data from each embodiment is summarised in the following table 2.
Embodiment 6
957 grams of carbon tetrachloride is added into reactor.Reaction temperature is maintained at 35 DEG C.Open UV lamp.After five minutes,
Feed the chloroform of 100 weight % with the rates of 5.30 gram/minutes, and with the rate of 3.42 gram/minutes by the chlorine of 100 weight %
It is bubbled in solution, lasts 90 minutes.Chlorine is fed with 112% for react required stoichiometry.Every 30 minutes
Sampling.The conversion ratio of chloroform is 98.90%, and chloroform is 99.94% to the selectivity of carbon tetrachloride, and surplus is to generate chlordene
The reaction chloroform of ethane.
Embodiment 7
953 grams of mixtures are added into reactor, the mixture contains 1.02% chloroform in carbon tetrachloride.It will
Reaction temperature is maintained at 35 DEG C.Open UV lamp.After five minutes, the chloroform of 100 weight % is fed with the rate of 5.78 gram/minutes, and
The chlorine of 100 weight % is bubbled in solution with the rate of 3.42 gram/minutes, lasts 90 minutes.Chlorine with fed chloroform into
100% of stoichiometry needed for row reacts is fed.It samples within every 30 minutes.The conversion ratio of chloroform is 97.79%, and chloroform
Selectivity to carbon tetrachloride is 99.84%, and surplus is the reaction chloroform for generating carbon trichloride.
Embodiment 8
1044 grams of mixtures are added into reactor, the mixture contains 8.93% chloroform in carbon tetrachloride.
Reaction temperature is maintained at 35 DEG C.Open UV lamp.After five minutes, the chloroform of 100 weight % is fed with the rate of 5.76 gram/minutes,
And the chlorine of 100 weight % is bubbled in solution with the rate of 3.42 gram/minutes, last 90 minutes.Chlorine is with fed chloroform
React required stoichiometry 100% is fed.It samples within every 30 minutes.The conversion ratio of chloroform is 90.99%, and chlorine
The imitative selectivity to towards carbon tetrachloride is 99.67%, and surplus is the reaction chloroform for generating carbon trichloride.
Embodiment 9
In this embodiment, borosilicate glass optical filter is taken out from lamp.963 grams of mixtures are added into reactor,
The mixture contains 1.24% chloroform in carbon tetrachloride.Reaction temperature is maintained at 35 DEG C.Open UV lamp.5 minutes
Afterwards, the chloroform of 100 weight % is fed with the rate of 5.78 gram/minutes, and with the rate of 3.42 gram/minutes by 100 weight %'s
Chlorine is bubbled in solution, lasts 90 minutes.Chlorine with fed chloroform react the 100% of required stoichiometry carry out into
Material.It samples within every 30 minutes.The conversion ratio of chloroform is 98.33%, and chloroform is 99.60% to the selectivity of carbon tetrachloride, remaining
Amount is the reaction chloroform for generating carbon trichloride.
Table 2
| Embodiment | 6 | 7 | 8 | 9 |
| Pounds Per Hour CHCl3/1000 pounds of CCl4 | 321 | 612 | 704 | 613 |
| Raw materials components mole ratio (Cl2:CHCl3) | 1.09 | 1.00 | 1.00 | 1.00 |
| Initial CHCl3 (weight %) in reactor | 0.00% | 1.02% | 8.93% | 1.24% |
| Temperature, DEG C | 35 | 35 | 35 | 35 |
| Borosilicate glass optical filter on lamp | It is | It is | It is | It is no |
| CHCl3 conversion ratio | 98.90% | 97.79% | 90.99% | 98.33% |
| To the selectivity of CCl4 | 99.94% | 99.84% | 99.67% | 99.60% |
It is in table 2 statistics indicate that, embodiment 7,8 and 9 is not belonging to practical framework of the invention because reaction to carbon tetrachloride
Selectivity have exceeded acceptable range.For example, because only obtaining 99.84% selectivity, gained produces in embodiment 7
Logistics comprises more than the carbon trichloride of 1500ppm, this for use carbon tetrachloride as most of synthetic methods of raw material for
It is unacceptable level.Therefore need to carry out product stream further distillation to remove carbon trichloride.Embodiment 7,8 and 9 quilts
Think due to there is excessive chloroform during the reaction and failure.
It will become without departing from the various modifications and variations of scope and spirit of the present invention to those skilled in the art
Obviously.The present invention should not be strictly limited to illustrative embodiments described in this paper.
Claims (20)
1. a kind of method for producing carbon tetrachloride, described method includes following steps:
(i) make chlorine and haloform reaction in the reaction mixture comprising chlorine, chloroform and carbon tetrachloride in the presence of electromagnetic radiation,
Wherein, relative to the weight of reaction mixture, the concentration of chloroform is less than 5000ppm by weight, which at least wraps
Chlorine containing the stoichiometric levels relative to chloroform, which generates chloro, and wherein reaction mixture fully mixes
It closes.
2. method as described in any one of the preceding claims, wherein relative to the weight of reaction mixture, the concentration of chloroform
It is less than 4000ppm by weight.
3. method as described in any one of the preceding claims, wherein on the basis of the overall weight of reaction mixture, reaction
Cl concn in mixture is the chlorine greater than 0.01 weight %.
4. method as described in any one of the preceding claims, wherein on the basis of the overall weight of reaction mixture, reaction
Cl concn in mixture is the chlorine greater than 0.1 weight %.
5. method as described in any one of the preceding claims, wherein the wavelength of the electromagnetic radiation is about 200 to about
500nm。
6. method as described in any one of the preceding claims, wherein during the reaction step, to reaction mixture into
To obtain turbulent flow, the turbulent flow can be quantified as the Reynolds number greater than 4000 for row stirring.
7. method as described in any one of the preceding claims, wherein the reaction step occurs in the reactor, described anti-
Answer device that about 10 DEG C to about 70 DEG C of temperature and about 0.8 atmosphere is maintained to be depressed into the pressure of about 15 atmospheric pressure.
8. method as described in any one of the preceding claims, wherein the reaction step is generated containing less than 1000ppm six
The crude product stream of chloroethanes.
9. method as described in any one of the preceding claims, wherein the reaction step consumption is greater than 99.00% chlorine
It is imitative.
10. a kind of method for producing carbon tetrachloride, described method includes following steps:
(i) reaction mixture is provided in reactor, wherein reaction mixture includes carbon tetrachloride, chlorine and chloroform；
(ii) make reaction mixture be subjected to electromagnetic energy, thus convert carbon tetrachloride at least part chloroform；
(iii) product stream is removed from reactor, wherein the product stream includes carbon tetrachloride；And (iv) in the removal
After the step of product stream, at least part product stream is returned in reactor.
11. method as described in any one of the preceding claims, wherein the merging step includes: with every less than 1000 pounds
The rate of carbon tetrachloride in hour every 1000 pounds of reactors, chloroform is introduced into reactor.
12. method as described in any one of the preceding claims, wherein the merging step includes: with every small less than 800 pounds
When every 1000 pounds of reactors in carbon tetrachloride rate, chloroform is introduced into reactor.
13. method as described in any one of the preceding claims, wherein the merging step includes: to be greater than 1.00:1.00
Chlorine and chloroform molar ratio, chlorine is introduced into reactor.
14. method as described in any one of the preceding claims, wherein the merging step includes: to be greater than 1.02:1.00
Chlorine and chloroform molar ratio, chlorine is introduced into reactor.
15. method as described in any one of the preceding claims, the method also includes following steps: stirring in reactor
Reaction mixture, to generate the well-mixed reactor close to ideal continuous stirred tank reactor.
16. method as described in any one of the preceding claims, the method also includes following steps: stirring in reactor
Reaction mixture, to provide the turbulent flow that quantization has about 4000 to about 30000 Reynolds numbers.
17. method as described in any one of the preceding claims, wherein the reaction mixture in reactor is maintained about 10 DEG C
The pressure of about 15 atmospheric pressure is depressed into about 70 DEG C of temperature and about 0.8 atmosphere.
18. method as described in any one of the preceding claims, wherein the wavelength of the electromagnetic radiation is about 200 to about
500nm。
19. method as described in any one of the preceding claims, wherein product stream includes the carbon trichloride less than 1000ppm,
And the chloroform amount in product stream shows that chloroform conversion ratio is greater than 99.00%.
20. making chlorine in the optical chlorinating reaction in the method for type for converting chloroform to by optical chlorinating reaction in carbon tetrachloride
Be subjected to ultraviolet light in the presence of chloroform, improvement is included in well-mixed reactor, comprising less than 5000ppm chloroform and
Optical chlorinating reaction is at least carried out in the carbon tetrachloride medium of the chlorine of stoichiometric levels, the reactor is about including being subjected to wavelength
The reaction zone of 200 to about 500nm electromagnetic radiation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662358340P | 2016-07-05 | 2016-07-05 | |
| US62/358,340 | 2016-07-05 | ||
| PCT/US2017/040426 WO2018009459A1 (en) | 2016-07-05 | 2017-06-30 | Photochlorination of chloroform to carbon tetrachloride |
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| CN109415281B CN109415281B (en) | 2022-04-26 |
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| US (3) | US10787405B2 (en) |
| EP (2) | EP3481797B1 (en) |
| JP (2) | JP7411330B2 (en) |
| CN (1) | CN109415281B (en) |
| CA (1) | CA3028445C (en) |
| ES (1) | ES2874144T3 (en) |
| MX (1) | MX2018016382A (en) |
| PT (1) | PT3481797T (en) |
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| PT3481797T (en) * | 2016-07-05 | 2021-05-13 | Occidental Chem Co | Photochlorination of chloroform to carbon tetrachloride |
| GB2575077A (en) | 2018-06-28 | 2020-01-01 | Domino Uk Ltd | Stroke direction offset adjustment |
| US11780792B2 (en) | 2019-01-10 | 2023-10-10 | Occidental Chemical Corporation | Photochlorination of partially-chlorinated chloromethanes to carbon tetrachloride |
| US11498046B2 (en) * | 2019-06-27 | 2022-11-15 | Phoseon Technology, Inc. | Method and system for tetrachloromethane synthesis |
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| JP2022050578A (en) | 2022-03-30 |
| MX2018016382A (en) | 2020-08-03 |
| US10787405B2 (en) | 2020-09-29 |
| EP3481797B1 (en) | 2021-03-31 |
| JP7411330B2 (en) | 2024-01-11 |
| US20190308918A1 (en) | 2019-10-10 |
| US11584703B2 (en) | 2023-02-21 |
| TWI756239B (en) | 2022-03-01 |
| PT3481797T (en) | 2021-05-13 |
| EP3481797A1 (en) | 2019-05-15 |
| EP3805188A1 (en) | 2021-04-14 |
| JP2019523243A (en) | 2019-08-22 |
| CA3028445C (en) | 2023-08-22 |
| JP7447159B2 (en) | 2024-03-11 |
| US20210009491A1 (en) | 2021-01-14 |
| ES2874144T3 (en) | 2021-11-04 |
| CN109415281B (en) | 2022-04-26 |
| CA3028445A1 (en) | 2018-01-11 |
| US20230202952A1 (en) | 2023-06-29 |
| WO2018009459A1 (en) | 2018-01-11 |
| TW201811721A (en) | 2018-04-01 |
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